EP0351603A2 - Réaction de transvinylation - Google Patents

Réaction de transvinylation Download PDF

Info

Publication number
EP0351603A2
EP0351603A2 EP89111829A EP89111829A EP0351603A2 EP 0351603 A2 EP0351603 A2 EP 0351603A2 EP 89111829 A EP89111829 A EP 89111829A EP 89111829 A EP89111829 A EP 89111829A EP 0351603 A2 EP0351603 A2 EP 0351603A2
Authority
EP
European Patent Office
Prior art keywords
vinyl
reaction
ruthenium
acid
grams
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP89111829A
Other languages
German (de)
English (en)
Other versions
EP0351603A3 (fr
EP0351603B1 (fr
Inventor
Rex Eugene Murray
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Corp filed Critical Union Carbide Corp
Publication of EP0351603A2 publication Critical patent/EP0351603A2/fr
Publication of EP0351603A3 publication Critical patent/EP0351603A3/fr
Application granted granted Critical
Publication of EP0351603B1 publication Critical patent/EP0351603B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18—Oxygen atoms
    • C07D263/20—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • a process for the transvinylation of a vinyl derivative of a Bronsted acid with a different Bronsted acid which comprises providing a liquid phase mixture containing said vinyl derivative and said Bronsted acid in the presence of a ruthenium compound at a temperature at which transvinylation occurs and recover­ing as a product of transvinylation the vinyl derivative of the different Bronsted acid.
  • the experimental portion discloses the use of only palladium on carbon, copper on carbon, iron on carbon, palladium/copper on carbon, palladium/copper/iron on silica, mercuric acetate on carbon, and mercuric chloride on carbon. Hg and Pd are cited, at col. 1, line 67, as the preferred metals. There is no recognition by this patentee of any special advantages to (i) the use of ruthenium compounds as catalysts for transvinylation reactions and (ii) effecting the reaction in a liquid phase reaction using a ruthenium compound as the catalyst.
  • the invention relates to a process for the transvinylation of a vinyl deriva­tive of a Bronsted acid (I) with a different Bronsted acid (II) which comprises providing a liquid phase mixture containing said vinyl derivative and said Bronsted acid (II) in the presence of a ruthenium compound at a temperature at which transvinylation occurs and recovering as a product of transvinylation the vinyl derivative of the different Bronsted acid (II).
  • the ruthenium is soluble in the reaction mixture in a catalytically effective amount.
  • Transvinylations are equilibrium reactions. The efficiency of the reaction is measured by the extent the desired transvinylation reaction product is present in the equilibrium reaction products. In other words, the reaction generates more than one product and the effectiveness of the process is frequently measured by the proportion of the desired product to the other products of the transvinylation reaction.
  • the reaction of the invention involves the combination of a vinyl derivative of a Bronsted acid (I); a different Bronsted acid (II) with which to interchange; a ruthenium compound; and liquid phase reaction conditions.
  • the Bronsted acid is any species which can act as a source of protons.
  • Suitable vinyl derivatives of a Bronsted acid (I) are vinyl acetate, vinyl pivalate, vinyl benzoate, vinyl methacrylate, vinyl acrylate, divinyl isophthalate, divinyl terephthalate, divinyl adipate, vinyl propionate, vinyl stearate, vinyl salicylate, vinyl cinnamate, vinyl 2-ethylhexanoate, vinyl cyclohexanoate, N-vinyl pyrrolidinone, N-vinylsuccinimide, vinyl phenyl ether, vinyl methyl ether, vinyl ethyl ether, N-vinyl 2-oxazolidinone, N-vinyl ethyleneurea, N-vinyl N-acetylethyleurea, 2-vinyloxyethyl acetate, 2-vinyloxyethyl pivalate, 2-vinyloxyethylacrylate, vinyl chloride, vinyl sulfate, ethyleneurea, N-
  • Preferred vinyl derivatives are the vinyl esters of carboxylic acids and the vinyl alkyl or aryl ethers, mainly because they are more commercially available.
  • Suitable Bronsted acids (II) for the practice of the invention are carboxylic acids such as monocarboxylic and polycarboxylic acids illustrated by acetic acid, propionic acid, butyric acid, pivalic acid and other neo acids, stearic acid, and other vinyl esters of fatty acids, benzoic acid, terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, malic acid, maleic acid, polyacrylic acids, crotonic acid, acrylic acid, methacrylic acid, salicylic acid, cinnamic acid, 2-­ethylhexanoic, and cyclohexanoic acid; amides such as 2-pyrrolidinone, 2-pyrrolidone, ⁇ -caprolactam, 2-oxazolidinone, ethyleneurea, N-acetyl ethyleurea, and succinimide; alcohols such as methanol, ethanol, n
  • the preferred Brondsted acids (II) are the carboxylic acids, the alcohols, the imines, the amides the imides, the phenolics, and the like.
  • transvinylation reactions that may be carried out by the process of the invention, are the following:
  • the process of this invention provides an excellent route to many hard to produce vinyl compounds because of the desirable physical and chemical properties of the ruthenium compounds which provide the basis for the catalytic reaction.
  • the ruthenium catalysts are easily obtainable as soluble components and can be used in the form of non-volatile compounds possessing high thermal stability, and exhibiting high catalytic activity only at elevated temperatures. Unlike palladium, the ruthenium-based catalyst does not lead to observable metal precipitation, even when reaction is conducted at temperatures above 150°C. From a practical standpoint, the physical and chemical properties of the ruthenium catalyst (soluble, non-volatile, and possessing high thermal stability) permit product removal by distillation. These properties suggest that the ruthenium catalyst system is far superior to prior art transvinylation technologies using palladium and mercury.
  • ruthenium compound to provide the catalytic activity for the transvinylation reaction is not narrowly critical. Essentially any ruthenium compound can be effectively employed to carry out the transvinylation reaction. However, the invention is believed to involve novel ruthenium-based catalysts which to promote the vinyl interchange (transvinylation) between vinyl derivatives and the Bronsted acids. It is believed the primary requirement for the generation of such catalysts and the requisite catalytic activity are ruthenium precursors to the catalyst which can be converted to [Ru(CO)2RCO2] or similar compounds even if the precursor during the reaction fails to be converted to such structures.
  • [Ru(CO)2RCO2] or similar compounds may not be the transvinyla­tion catalyst of the invention but it has been noted that the use of such compounds assures the effective catalytic reaction and the results herein characterized.
  • the process of this invention may be practiced with a vast array of ruthenium compounds. Even instances where the ruthenium compound is too stable for catalyzing the reaction, catalysis can be effected by including a compound which does not adversely affect the transvinylation reaction and stimulates the ruthenium compound to be converted to a species having catalytic activity.
  • ruthenium chloride is a sluggish catalyst but is made quite active by the addition of an alkali such as an alkali metal salt of a carboxylic acid, viz.
  • the precursor compounds may range from supported ruthenium such as ruthenium on carbon, alumina, and the like, to ruthenium carbonyl to bis(eta - 5-cyclooctadienyl)ruthenium(II)/tri-n-­butylphosphine and to bis(eta 5-cyclooctadienyl)ruthenium(II)/trialkyl- phosphine/­maleic anhydride.
  • supported ruthenium such as ruthenium on carbon, alumina, and the like
  • the precursor compounds may range from supported ruthenium carbonyl to bis(eta - 5-cyclooctadienyl)ruthenium(II)/tri-n-­butylphosphine and to bis(eta 5-cyclooctadienyl)ruthenium(II)/trialkyl- phosphine/­maleic anhydride.
  • the most preferred catalysts are formed from ruthenium carbonyl carboxy­lates, or precursors which can convert into these species. Based on an analysis of the literature, certain assumptions of the likely structure of the catalyst have been made. Based on the recognition that ruthenium carbonyl reacts with carboxylic acids to produce soluble orange-yellow complexes possessing the empirical formula [Ru(­CO)2RCO2] n and the fact these complexes appear sufficiently labile to accommodate coordination of vinyl acetate and subsequently catalyze exchanges between vinyl-­bound and ruthenium-bound carboxylates, it is believed that such structures are involved in the catalysis for the transvinylation process.
  • Ruthenium(III) chloride, ruthenium(III) iodide, tris(2,2-­bipyridyl)ruthenium(II) chloride hexahydrate, and ruthenocene exhibited only very slight catalytic activity, which further substantiates that the level of catalyst activity intimately depends upon the form of the ruthenium precursor.
  • the presumed catalyst precursor, [Ru(CO)2RCO2] n can be generated in several ways.
  • the trinuclear complex, [Ru3O(OAc)6(H2O)3]OAc gives an efficient transvinylation catalyst.
  • Infrared analysis indicates that [Ru3O(OAc)6(H2O)3]OAc can convert to [Ru(CO)2RCO2] n under transvinylation reaction conditions. This is even observed when the reaction is conducted under nitrogen atmosphere, rather than carbon monoxide. Frequently, there is sufficient adventitious carbon monoxide available to in situ convert all of the Ru to a carbonyl form.
  • ruthenium trihalide-based precursors e.g., ruthenium(III) chloride and ruthenium(III) iodide
  • exhibit only slight activity e.g., ruthenium(III) chloride and ruthenium(III) iodide
  • a very active and more selective catalyst can be generated in situ from ruthenium chloride and sodium acetate. This presumably produces the [Ru3O(OAc)6(H2O)3]OAc precursor and insoluble sodium chloride salt.
  • the condi­tions useful for effective catalyst generation includes a ruthenium carboxylate precursor or a mixture of reagents which can generate a ruthenium carboxylate precursor.
  • ruthenium halide precursors can be used in the invention, however they are best under in conjunction with alkali metal carboxylates (typically sodium acetate) to facilitate precipitation of the alkali metal halide (typically sodium chloride).
  • alkali metal carboxylates typically sodium acetate
  • Non-carbonyl and non-carboxylate containing ruthenium compounds can also lead to highly active catalysts.
  • ruthenium­(III) acetyl-acetonate, ruthenium(IV) oxide, ruthenium on carbon, and ruthenium on alumina have all shown catalytic activity. Under these conditions, ruthenium powder shows trace activity.
  • a route to transvinylation catalysts from ruthenium halides involves, as pointed above, displacing the halide from the ruthenium precursor. It is also likely that other metal salts, known to precipitate halides (Ag+, Cu+, Hg+) would also be effective in combination with ruthenium halides to provide the catalyst precursor.
  • the amount of the ruthenium catalyst useful for effecting the transvinyla­tion reaction is not narrowly critical.
  • the typical amount is a catalytically effective amount, that is, an amount which is sufficient to effect the desired vinyl interchange.
  • ruthenium catalyst concentrations ranging roughly from 30,000 parts to 0.5 part per million (ppm) ruthenium based on the weight of the liquid phase reaction medium can be used to effect the reaction. It is believed that larger and smaller amounts of the catalyst may be used to effect the reaction.
  • the most preferred range is from 0.1 ppm to 500 ppm ruthenium, same basis.
  • the transvinylation reaction be carried out in the absence of an amount of water in the reaction mixture that inhibits the production of the desired vinyl interchanged product.
  • the reaction can be carried out in the presence of significant quantities of water.
  • the inhibiting effects of water are reactant dependent.
  • Increasing the concentration of ruthenium catalyst in the reaction mixture is a facile method of overcoming water inhibition in many cases, if not most cases. It has been noted that these is a correla­tion between the amount of ruthenium catalyst employed and the amount of water usuable in the process. The more ruthenium present, the more water that may be present in the reaction without adversely affecting the reaction. It is desirable to use a system which is substantially water-free.
  • the amount of water present in the reaction is desirably less than about 25 weight % of the weight of the reaction mixture.
  • the amount of water in the reaction is less than about 15 weight % of the weight of the mixture.
  • Essentially anhydrous reaction systems as herein characterized are preferred.
  • the amount of water in the reaction is less than about 5 weight % of the weight of the mixture, more preferably less than about 2.5 weight % of the weight of the mixture, most preferably less than about 1 weight % of the weight of the mixture.
  • Water concentration in the reaction mixture can be controlled by conventional procedures, such as by drying the reactants carefully, azeotropically distilling the water from the reaction when an azeotrope is formed, and by the addition of molecular sieve drying agent.
  • the temperature at which the reaction can be carried out is also not narrowly critical.
  • the reaction rate varies with the identity of the Bronsted acid to be transvinylated. The more acidic acids tend to the reactive at lower temperatures. It is also desirable to operate at a temperature at which the acid reactant is dissolved or liquid. The process is favorably effected by keeping the reaction temperature below the boiling point of the highest boiling reactant or at sufficient pressure to maintain the liquid state.
  • the liquid phase condition can best be accomplished by operating at temperatures above the melting point of the acid. Nonetheless, terephthalic acid (mp > 300°C), which is insoluble in most catalyst-compatible solvents, was transvinylated to divinyl terephthalate by conducting the reaction in aromatic ester solvents at elevated temperatures (ca. 150°C). These conditions presumably facilitate transvinylation by achieving slight solubility of the terephthalic acid.
  • the temperature at which the reactions may be carried out range from 20°C to 300°C, but 50°C to 200°C is more preferred.
  • the optimum reaction conditions depend chiefly on the Bronsted acid (such as a carboxylic acid) to be transvinylated. If the acid is soluble at the reaction temperature, it is better to operate without solvent. It is also preferred, when feasible, to conduct the reaction at temperatures above the melting point of the acid.
  • the Bronsted acid such as a carboxylic acid
  • Transvinylation works best without solvents or in nonpolar solvents. Suitable results have been achieved in solvents such as toluene, heptane, silicone oil, mineral oil, phenylbenzoate, dimethylterephthalate, and dioctylphthalate. More highly polar solvents such as alcohols, water, sulfolane, Carbowaxes®, and N-­methylpyrolidinone tend to inhibit reaction rates. Oxygenated aromatics such as diphenylether, methylbenzoate, dimethylterephthalate, and dioctylphthalate are desirable solvents in the synthesis of divinylterephthalate and divinylisophthalate.
  • solvents such as toluene, heptane, silicone oil, mineral oil, phenylbenzoate, dimethylterephthalate, and dioctylphthalate.
  • More highly polar solvents such as alcohols, water, sulfolane, Carbowaxes®, and N-­methyl
  • the invention is operational over a broad range of mole ratios of Bronsted acid (such as carboxylic acid) to vinyl derivative.
  • the preferred ratio depends mostly on the transformation sought. In general, ratios of 100/1 to 1/100 are preferred and ratios of 1/10 to 10/1 are most preferred.
  • the mole ratio of the Bronsted acid (viz., carboxylic acid or carboxylate) to ruthenium should be at least 0.5 to 1.
  • the ruthenium concentration in the reaction mixture is a catalytically effective amount and this is typically in the parts per million range while the acid is typically a major component of the reaction mixture.
  • Most preferably the mole ratio of Bronsted acid to ruthenium is 50/1 to 1,000,000/1.
  • reaction atmospheres such as carbon monoxide, air, nitrogen and ethylene
  • Nitrogen and ethylene are suitable in most situations.
  • Carbon monoxide appears to improve catalyst selectivity.
  • Air has been employed in conjuction with phenothiazine (polymerization inhibitor) for the synthesis of vinyl acrylates.
  • the catalytic reaction produces small amounts of methane, carbon monoxide, and carbon dioxide by-products which obviously augment the initially charged reaction atmosphere.
  • the reaction may be carried out at pressures which are subatmospheric, atmospheric or superatmospheric. In some situations, reaction can also be conducted under vacuum, such as in a distillation apparatus.
  • a desirable reaction pressure is from 1.33 ⁇ 5 mbar (10 ⁇ 6 torr) to 345 bar.abs. (5,000 psia).
  • the more desirable reaction pressure is from 1.33 ⁇ 4 mbar (10 ⁇ 5 torr) to 55 bar.abs. (800 psia).
  • the preferred reaction pressure is from 1.33.10 ⁇ 3 mbar (10 ⁇ 4 torr) to 38 bar.abs. (550 psia).
  • the preferred reaction pressure is superatmospheric pressure, typically from 1.1-345 bar.abs. (16 to 5,000 psia).
  • reaction is carried out under conditions at which all of the reactants are in the liquid phase. This does not require that the reaction environment be wholly in the liquid phase. It simply means that sufficient of the reactants and the catalyst be in the liquid phase that the reaction can occur in the liquid phase.
  • solid ruthenium on a solid support can be used as a catalyst precursor. In the presence of reactant, solvent and/or carbon monoxide, sufficient ruthenium can be converted to a liquid soluble compound such that the catalytic reaction is attainable.
  • reactant can be supplied in a super-­critical fluid condition which is sufficiently "liquid" to support the liquid phase conditions of this invention. Much of the reaction system can be in the gas or solid phase, and this would be acceptable so long as enough of the reaction system is in the liquid phase to support the transvinylation reaction of the invention.
  • a favorable aspect of the process of the invention is to shift the equilibrium of the reaction in the direction of the favored product so that higher concentrations of the product can be obtained based on the amount of starting materials employed. This can be done by the continuous removal of one of the products of the reaction so as to shift the equilibrium in a favorable direction without adversely affecting the catalyst and/or the ruthenium values.
  • Vinyl pivalate (91 pounds) was prepared in two, 75,7l (20 gallon)-batch runs in a 113.5l (30 gallon) stainless steel reactor.
  • pivalic acid 34 kg (75.5 lbs), 37.8l (10 gallons) and vinyl acetate 35 kg (77.9 lbs), 37.8l (10 gallons) were transvinylated in the presence of 300 ppm ruthenium catalyst, described in the proceeding paragraph, at 145°C using a 3.45 bar (50 psig) carbon monoxide reaction atmosphere for 5 hours.
  • Reaction product was removed from the reactor by vacuum distillation (60-130°C, -320 mbar-240 mm Hg) from the ruthenium catalyst without difficulty.
  • Catalytic activity of numerous ruthenium precursor compounds was evaluated according to the following procedure.
  • a mixture of the ruthenium com­pound, vinyl acetate (17.2 grams), benzoic acid (12.2 grams) and nonane (internal standard for gas chromatographic analysis) were charged to a Fischer-Porter bottle, sealed, purged three times with carbon monoxide and finally pressurized to 1.7 bar (25 psig).
  • the magnetically-stirred reaction mixture was heated in an oil bath to the desired reaction temperature for a specified time period (both specified in the table).
  • Gas chromatographic analysis on a DB-1 fused silica capillary column (30M) revealed the amount of vinyl benzoate formed by transvinylation (shown in the table).
  • the following table demonstrates transvinylations without product isolation.
  • ruthenium catalyzed transvinylations 300 ppm ruthenium
  • VA ether vinyl acetate
  • VP vinyl pivalate
  • trans-cinnamic acid 148 grams, 1 mole
  • vinyl acetate 172 grams, 2 moles
  • ruthenium carbonyl ruthenium carbonyl
  • Example 62 the vinyl acetate of Example 62 was azeotropically dried prior to use.
  • the crude vinyl acetate was dried by azeotropic refluxing on a Dean-­Stark apparatus for several hours.
  • the "anhydrous" crude vinyl acetate (5.0 grams), propionic acid (25.0 grams), nonane standard (0.4398 grams) and ruthenium carbonyl (0.019 grams, 300 ppm Ru) were charged to a Fischer-Porter bottle, purged and pressurized to 1.7 bar (25 psig) carbon monoxide and heated 3 h at 140°C and sample.
  • the following products are tabulated vinyl acetate 1.290 grams acetic acid 0.468 grams vinyl propionate 3.249 grams

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Saccharide Compounds (AREA)
  • Furan Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pyrrole Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Catalysts (AREA)
EP89111829A 1988-06-30 1989-06-29 Réaction de transvinylation Expired - Lifetime EP0351603B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/213,697 US4981973A (en) 1988-06-30 1988-06-30 Transvinylation reaction
US213697 1988-06-30

Publications (3)

Publication Number Publication Date
EP0351603A2 true EP0351603A2 (fr) 1990-01-24
EP0351603A3 EP0351603A3 (fr) 1991-11-21
EP0351603B1 EP0351603B1 (fr) 1994-12-07

Family

ID=22796150

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89111829A Expired - Lifetime EP0351603B1 (fr) 1988-06-30 1989-06-29 Réaction de transvinylation

Country Status (19)

Country Link
US (1) US4981973A (fr)
EP (1) EP0351603B1 (fr)
JP (1) JPH0684317B2 (fr)
KR (1) KR950000643B1 (fr)
AT (1) ATE115113T1 (fr)
AU (1) AU623151B2 (fr)
BR (1) BR8903207A (fr)
CA (1) CA1337869C (fr)
DE (1) DE68919766T2 (fr)
DK (1) DK324889A (fr)
ES (1) ES2064385T3 (fr)
FI (1) FI893186A (fr)
HU (1) HU208519B (fr)
MC (1) MC2036A1 (fr)
MY (1) MY105046A (fr)
NO (1) NO173275C (fr)
RO (1) RO105609B1 (fr)
RU (1) RU2051143C1 (fr)
ZA (1) ZA894954B (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497340A2 (fr) * 1991-01-31 1992-08-05 Union Carbide Chemicals & Plastics Technology Corporation Procédé de transvinylation par distillation réactive
EP0506070A3 (en) * 1991-03-28 1993-05-12 Union Carbide Chemicals & Plastics Technology Corporation Transvinylation process for the preparation of thermally labile vinyl compounds and vinyl compounds prepared from thermally labile acids
US5214172A (en) * 1991-05-06 1993-05-25 Air Products And Chemicals, Inc. Catalytic transvinylation of vinyl esters
EP0752417A1 (fr) * 1995-07-06 1997-01-08 Basf Aktiengesellschaft Procédé de préparation de N-alkénylurées
EP0761655A1 (fr) * 1995-09-08 1997-03-12 Basf Aktiengesellschaft Procédé de préparation d'ester d'acide N-alkenylcarbamique
DE102012002274A1 (de) 2012-02-06 2013-08-08 Oxea Gmbh Verfahren zur Koppelproduktion von Vinylestern und Essigsäurefolgeprodukten oder Propionsäurefolgeprodukten
DE102012002282A1 (de) 2012-02-06 2013-08-08 Oxea Gmbh Verfahren zur Herstellung von Vinylestern
WO2013137997A1 (fr) * 2012-03-15 2013-09-19 Rohm And Haas Company Procédé de transestérification
DE102013224496A1 (de) 2013-11-29 2015-06-03 Wacker Chemie Ag Verfahren zur Ruthenium-katalysierten Umvinylierung von Carbonsäuren
DE102013224491A1 (de) 2013-11-29 2015-06-03 Wacker Chemie Ag Verfahren zur Ruthenium-katalysierten Umvinylierung von Carbonsäuren
DE102014206916A1 (de) 2014-04-10 2015-10-15 Wacker Chemie Ag Verfahren zur Ruthenium-katalysierten Umvinylierung von Carbonsäuren
DE102014206915A1 (de) 2014-04-10 2015-10-15 Wacker Chemie Ag Verfahren zur Darstellung einer aktiven Ruthenium-Katalysatorlösung für die Umvinylierung von Carbonsäuren
WO2021122249A1 (fr) * 2019-12-20 2021-06-24 Basf Se Synthèse de composés n-vinyliques par réaction de composés nh- cyliques avec de l'acétylène en présence d'un catalyseur homogène

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2786104B2 (ja) * 1994-02-28 1998-08-13 日本電気株式会社 半導体装置
US5741925A (en) * 1997-01-13 1998-04-21 Air Products And Chemicals, Inc. Transvinylation of naphthenic acids
US6133228A (en) 1998-05-28 2000-10-17 Firmenich Sa Slow release of fragrant compounds in perfumery using 2-benzoyl benzoates, 2-alkanoyl benzoates or α-keto esters
JP4856826B2 (ja) * 2001-08-30 2012-01-18 株式会社ダイセル ビニルエーテル化合物の製造法
JP4804965B2 (ja) * 2006-03-10 2011-11-02 ダイセル化学工業株式会社 ビニル又はアリル基含有化合物の製造法
JP5312133B2 (ja) * 2009-03-26 2013-10-09 丸善石油化学株式会社 高純度ビニルエーテルの製造法
CN102958899B (zh) 2010-05-04 2015-12-02 塞拉尼斯国际公司 羧酸与乙酸乙烯酯的半连续乙烯基转移方法
DE102014210835A1 (de) 2014-06-06 2015-12-17 Wacker Chemie Ag Verfahren zur Trennung von hochsiedenden Carbonsäurevinylester/Carbonsäure-Gemischen
DE102015216373A1 (de) 2015-08-27 2017-03-02 Wacker Chemie Ag Verfahren zur katalytischen Umvinylierung von Carbonsäuren

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1304569A (fr) * 1961-10-27 1962-09-21 Consortium Elektrochem Ind Procédé de préparation d'esters vinyliques

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3188319A (en) * 1965-06-08 Production of vinyl estess
US2245131A (en) * 1941-06-10 Process of preparing vinyl esters
US2299862A (en) * 1942-10-27 Preparation of vinyl esters
US827718A (en) * 1905-12-02 1906-08-07 Benno Vom Eigen Shaving device.
US877103A (en) * 1907-07-12 1908-01-21 John Marsden Rotary engine.
US2997494A (en) * 1956-08-27 1961-08-22 Air Reduction Method of preparing vinyl esters of carboxylic acids
US2989554A (en) * 1957-01-30 1961-06-20 Vinyl Products Ltd Manufacture of vinyl esters
US3000918A (en) * 1958-05-15 1961-09-19 Grace W R & Co Vinyl ester synthesis
US3179641A (en) * 1961-05-22 1965-04-20 Armour & Co Vinyl aryl stearates and polymers thereof
US3117145A (en) * 1961-08-31 1964-01-07 Grace W R & Co Method of purifying vinyl esters of organic carboxylic acids
NL291243A (fr) * 1962-04-25 1900-01-01
US3158633A (en) * 1962-07-02 1964-11-24 William S Port Process for preparation of vinyl esters
DE1249847B (de) * 1964-12-22 1967-09-14 Deutsche Gold- und Silber Schei deanstalt vormals Roessler Frankfurt/M Verfahren zur Herstellung von a- und ß-Fornrylisobuttersaure estern und von a- und ß-Formylisobuttersaurenitnl durch Hydroformvlierung
US3337611A (en) * 1965-04-12 1967-08-22 Exxon Research Engineering Co Synthesis of vinyl esters by ester interchange with a molar excess of the carboxylicacid
US3391130A (en) * 1965-10-01 1968-07-02 Interchem Corp Vinyl-tris-(chloromethyl)-acetate and homopolymer
US3454644A (en) * 1966-05-09 1969-07-08 Shell Oil Co Homogeneous hydrogenation process employing a complex of ruthenium or osmium as catalyst
DE1296138B (de) * 1967-03-03 1969-05-29 Hoechst Ag Verfahren zur Herstellung von Carbonsaeurevinylestern
US3647832A (en) * 1967-03-23 1972-03-07 Rhone Poulenc Sa Ruthenium complexes and processes for their preparation
US3560534A (en) * 1967-08-01 1971-02-02 Exxon Research Engineering Co Transvinylation using mercuric acetate/perchloric acid catalyst
US3751449A (en) * 1969-06-26 1973-08-07 Minnesota Mining & Mfg Cycloaliphatic and phenylalkyl acrylates and vinyl esters
GB1326012A (en) * 1969-07-14 1973-08-08 Johnson Matthey Co Ltd Catalyst compositions
US3755387A (en) * 1969-08-05 1973-08-28 Dow Chemical Co Vapor phase transvinylation process
US3786102A (en) * 1971-08-09 1974-01-15 Grace W R & Co Transvinylation catalyst
GB1405592A (en) * 1971-08-11 1975-09-10 Johnson Matthey Co Ltd Compounds of ruthenium
US3965156A (en) * 1974-02-04 1976-06-22 General Electric Company Process for preparing vinyl esters of carboxylic acids
US3965155A (en) * 1974-02-04 1976-06-22 General Electric Company Process for preparing vinyl esters of carboxylic acids
US4112235A (en) * 1976-10-28 1978-09-05 Uop Inc. Transesterification of carboxylic acids
US4175056A (en) * 1977-11-04 1979-11-20 Uop Inc. Activated multimetallic catalytic composite comprising pyrolized ruthenium carbonyl
DE3172522D1 (en) * 1980-07-17 1985-11-07 Ciba Geigy Ag Vinyl-substituted 2,2'-bipyridines, polymers prepared therefrom, their preparation and their use
DE3047347A1 (de) * 1980-12-16 1982-07-22 Wacker-Chemie GmbH, 8000 München Palladium(ii)-katalysator, seine herstellung und verwendung
US4446073A (en) * 1981-08-05 1984-05-01 Uop Inc. Process for the reduction of unsaturated carboxylic acids
US4366259A (en) * 1981-10-29 1982-12-28 Texaco, Inc. Production of acetic acid and propionic acid and their esters
US4640802A (en) * 1981-12-10 1987-02-03 Shell Oil Company Process for the co-production of carboxylic acids and carboxylic acid esters
US4664851A (en) * 1981-12-30 1987-05-12 Shell Oil Company Process for the co-production of carboxylic acids and carboxylic acid esters
US4458088A (en) * 1982-04-01 1984-07-03 The Standard Oil Company (Sohio) Continuous process for the extraction and esterification of carboxylic acid
GB8406126D0 (en) * 1984-03-08 1984-04-11 Bp Chem Int Ltd Esters
GB8602178D0 (en) * 1986-01-29 1986-03-05 Shell Int Research Preparation of diester of 2-butenedioic acid

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1304569A (fr) * 1961-10-27 1962-09-21 Consortium Elektrochem Ind Procédé de préparation d'esters vinyliques

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497340A2 (fr) * 1991-01-31 1992-08-05 Union Carbide Chemicals & Plastics Technology Corporation Procédé de transvinylation par distillation réactive
EP0497340A3 (en) * 1991-01-31 1993-05-12 Union Carbide Chemicals & Plastics Technology Corporation Transvinylation process by reactive distillation
EP0506070A3 (en) * 1991-03-28 1993-05-12 Union Carbide Chemicals & Plastics Technology Corporation Transvinylation process for the preparation of thermally labile vinyl compounds and vinyl compounds prepared from thermally labile acids
US5214172A (en) * 1991-05-06 1993-05-25 Air Products And Chemicals, Inc. Catalytic transvinylation of vinyl esters
EP0752417A1 (fr) * 1995-07-06 1997-01-08 Basf Aktiengesellschaft Procédé de préparation de N-alkénylurées
US5639890A (en) * 1995-09-08 1997-06-17 Basf Aktiengesellschaft Preparation of N-akenylcarbamic esters
EP0761655A1 (fr) * 1995-09-08 1997-03-12 Basf Aktiengesellschaft Procédé de préparation d'ester d'acide N-alkenylcarbamique
DE102012002274A1 (de) 2012-02-06 2013-08-08 Oxea Gmbh Verfahren zur Koppelproduktion von Vinylestern und Essigsäurefolgeprodukten oder Propionsäurefolgeprodukten
DE102012002282A1 (de) 2012-02-06 2013-08-08 Oxea Gmbh Verfahren zur Herstellung von Vinylestern
WO2013117295A1 (fr) 2012-02-06 2013-08-15 Oxea Gmbh Transvinylation comme première étape d'une production couplée d'esters de vinyle et de produits réactionnels d'acide acétique ou d'acide propionique
WO2013117294A1 (fr) 2012-02-06 2013-08-15 Oxea Gmbh Procédé de préparation d'esters de vinyle
US9174921B2 (en) 2012-02-06 2015-11-03 Oxea Gmbh Transvinylation as a first stage of coupling production of vinyl esters and acetic acid or propionic acid reaction products
US9174922B2 (en) 2012-02-06 2015-11-03 Oxea Gmbh Method for producing vinyl esters
WO2013137997A1 (fr) * 2012-03-15 2013-09-19 Rohm And Haas Company Procédé de transestérification
WO2015078747A1 (fr) * 2013-11-29 2015-06-04 Wacker Chemie Ag Procédé de transvinylation catalysée par ruthénium d'acides carboxyliques
CN105793232B (zh) * 2013-11-29 2017-09-15 瓦克化学股份公司 钌催化的羧酸的乙烯基转移的方法
CN105793231B (zh) * 2013-11-29 2017-09-15 瓦克化学股份公司 钌催化的羧酸的乙烯基转移的方法
WO2015078746A1 (fr) 2013-11-29 2015-06-04 Wacker Chemie Ag Procédé de transvinylation catalysée par ruthénium d'acides carboxyliques
CN105793231A (zh) * 2013-11-29 2016-07-20 瓦克化学股份公司 钌催化的羧酸的乙烯基转移的方法
DE102013224491A1 (de) 2013-11-29 2015-06-03 Wacker Chemie Ag Verfahren zur Ruthenium-katalysierten Umvinylierung von Carbonsäuren
DE102013224496A1 (de) 2013-11-29 2015-06-03 Wacker Chemie Ag Verfahren zur Ruthenium-katalysierten Umvinylierung von Carbonsäuren
CN105793232A (zh) * 2013-11-29 2016-07-20 瓦克化学股份公司 钌催化的羧酸的乙烯基转移的方法
DE102014206915A1 (de) 2014-04-10 2015-10-15 Wacker Chemie Ag Verfahren zur Darstellung einer aktiven Ruthenium-Katalysatorlösung für die Umvinylierung von Carbonsäuren
US9695104B2 (en) 2014-04-10 2017-07-04 Wacker Chemie Ag Process for ruthenium-catalyzed transvinylation of carboxylic acids
WO2015154979A1 (fr) * 2014-04-10 2015-10-15 Wacker Chemie Ag Procédé de vinylisation d'acides carboxyliques catalysée par le ruthénium
DE102014206916A1 (de) 2014-04-10 2015-10-15 Wacker Chemie Ag Verfahren zur Ruthenium-katalysierten Umvinylierung von Carbonsäuren
US9782752B2 (en) 2014-04-10 2017-10-10 Wacker Chemie Ag Method for providing an active ruthenium catalyst solution for the transvinylation of carboxylic acids
WO2021122249A1 (fr) * 2019-12-20 2021-06-24 Basf Se Synthèse de composés n-vinyliques par réaction de composés nh- cyliques avec de l'acétylène en présence d'un catalyseur homogène

Also Published As

Publication number Publication date
NO892717L (no) 1990-01-02
CA1337869C (fr) 1996-01-02
AU623151B2 (en) 1992-05-07
EP0351603A3 (fr) 1991-11-21
KR910000589A (ko) 1991-01-29
ES2064385T3 (es) 1995-02-01
ZA894954B (en) 1990-04-25
NO173275B (no) 1993-08-16
BR8903207A (pt) 1990-02-13
HU208519B (en) 1993-11-29
NO173275C (no) 1993-11-24
DK324889A (da) 1989-12-31
KR950000643B1 (ko) 1995-01-26
JPH0684317B2 (ja) 1994-10-26
NO892717D0 (no) 1989-06-29
DE68919766T2 (de) 1995-05-04
ATE115113T1 (de) 1994-12-15
DK324889D0 (da) 1989-06-29
AU3717789A (en) 1990-01-04
FI893186A (fi) 1989-12-31
JPH0256438A (ja) 1990-02-26
FI893186A0 (fi) 1989-06-29
MY105046A (en) 1994-07-30
HUT50754A (en) 1990-03-28
US4981973A (en) 1991-01-01
RO105609B1 (ro) 1992-10-30
EP0351603B1 (fr) 1994-12-07
RU2051143C1 (ru) 1995-12-27
DE68919766D1 (de) 1995-01-19
MC2036A1 (fr) 1990-05-30

Similar Documents

Publication Publication Date Title
EP0351603B1 (fr) Réaction de transvinylation
US5210207A (en) Transvinylation process by reactive distillation
US4690912A (en) Rhodium-containing carbonylation catalysts with halogen-containing promoter
US5155253A (en) Transvinylation process for the preparation of thermally labile vinyl compounds and for vinyl compounds prepared from thermally labile acids
JP6217653B2 (ja) α，α−ジフルオロアセトアルデヒドの製造方法
EP0891320A1 (fr) Procede de production de 1,2-bis(acyloxylates)
JP2013209356A (ja) α−フルオロアルデヒド類の製造方法
JP2004531576A5 (fr)
WO1992009554A1 (fr) Technique de transvinylation assistee par un procede azeotropique
KR20000017100A (ko) α-케토카복실산 에스테르의 에스테르 교환방법
US5663422A (en) Process for the production of 1,2-diacetoxy esters
EP0689529B1 (fr) Procede de carbonylation de composes acetyleniquement insatures
US4355173A (en) Process for the preparation of alkyl carboxylate
EP1193238A1 (fr) Procédé pour la préparation de 2,4,5-trialkylbenzaldehydes
JPS60258142A (ja) 安息香酸の精製法
EP0165168A2 (fr) Procédé de carbonylation pour la préparation d'acides aromatiques et de leurs dérivés
JP3785479B2 (ja) ジアルキルカーボネートの製造方法
JPS6038035A (ja) グリコ−ルアルデヒドの製法及びその触媒
JPH06239796A (ja) ハロゲン酢酸ビニルエステルの製造方法
JPH06298716A (ja) ウレタノエステルの製造法
JP2003183225A (ja) エポキシドから３−ヒドロキシエステルを製造する方法
JPH1072433A (ja) 複素環含有（メタ）アクリル酸エステルの製造方法
JPH05201927A (ja) ビニルオキシカルボン酸エステルの製造法
JPH06135892A (ja) カルボン酸ビニルエステルの製造方法
JPS6322045A (ja) ケトンの製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19901231

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19930528

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19941207

REF Corresponds to:

Ref document number: 115113

Country of ref document: AT

Date of ref document: 19941215

Kind code of ref document: T

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 68919766

Country of ref document: DE

Date of ref document: 19950119

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2064385

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3014495

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19950629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19950630

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19950630

Ref country code: LI

Effective date: 19950630

Ref country code: CH

Effective date: 19950630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3014495

EUG Se: european patent has lapsed

Ref document number: 89111829.1

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960322

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960329

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960502

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960617

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970630

Ref country code: BE

Effective date: 19970630

BERE Be: lapsed

Owner name: UNION CARBIDE CORP.

Effective date: 19970630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000503

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030314

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20030318

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050101

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050629